Polymers prepared from imide containing dianhydrides

Abstract

Thermoplastic imide polymers prepared from a dianhydride monomer containing imide linkages and at least two cyclic anhydride groups and an aromatic diamine such as 4,4'-diaminodiphenyl ether. Comonomers such as 3,4:3', 4'-benzophenonecarboxylic dianhydride may be added. Preferably said dianhydride monomer containing imide linkages is made by reacting 4-aminophthalic acid with a dianhydride containing at least two cyclic anhydride groups, preferably in the ratio of about 2:1. Preferably said imide polymer is made by first forming a solution containing the diamine and adding the dianhydride monomer containing imide linkages while the temperature of the solution is maintained between 50 DEG and 120 DEG C. and most preferably at 110 DEG C.

1. A polymer containing imide linkages corresponding to that prepared by reacting a dianhydride component comprising (A) an aromatic dianhydride monomer containing two imide linkages, two terminal cyclic anhydride groups and two trivalent benzene radicals, the carbonyl groups of a cyclic anhydride and a nitrogen of an imide linkage attached to each of said radicals, the former attached to 1,2-positions of the radical, the latter 
     
     
       2. A polymer containing imide linkages as claimed in claim 1 wherein said 
     
     
       3. A polymer containing imide linkages as claimed in claim 1 wherein said aromatic dianhydride monomer is prepared by reacting 4-aminophthalic acid 
     
     
       4. A polymer containing imide linkages as claimed in claim 3 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 2,3:6,7-naphthalene tetracarboxylic dianhydride, 1,8:4,5-naphthalene tetracarboxylic dianhydride 1,2:5,6-naphthalene tetracarboxylic dianhydride, 3,4:3',4'-diphenyltetracarboxylic dianhydride, 2,3:2',3'-diphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, and 
     
     
       5. A polymer containing imide linkages as claimed in claim 3 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 1,2:4,5 benzenetetracarboxylic dianhydride and 
     
     
       6. A polymer containing imide linkages as claimed in claim 3 wherein the mole ratio of said 4-aminophthalic acid said dianhydride containing two 
     
     
       7. A polymer containing imide linkages derived by reacting (a) an aromatic dianhydride monomer containing two imide linkages, two terminal cyclic anhydride groups and two trivalent benzene radicals, the carbonyl groups of a cyclic anhydride and a nitrogen of an imide linkage attached to each of said radicals, the former attached to 1,2-positions of the radical, the latter attached to the 4-position of the radical and (b) 
     
     
       8. A polymer containing imide linkages as claimed in claim 7 wherein said aromatic dianhydride monomer is derived by reacting 4-aminophthalic acid 
     
     
       9. A polymer containing imide linkages as claimed in claim 8 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 2,3:6,7-naphthalene tetracarboxylic dianhydride, 1,8:4,5-naphthalene tetracarboxylic dianhydride, 1,2:5,6-naphthalene tetracarboxylic dianhydride, 3,4:3',4'-diphenyl tetracarboxylic dianhydride, 2,3:2',3'-diphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, and 
     
     
       10. A polymer containing imide linkages as claimed in claim 8 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 1,2:4,5 benzenetetracarboxylic dianhydride and 
     
     
       11. A polymer containing imide linkages as claimed in claim 8 wherein the mole ratio of said 4-aminophthalic acid to said dianhydride containing two 
     
     
       12. A polymer containing imide linkages corresponding to that prepared by reacting (1) (a) an aromatic dianhydride monomer containing two imide linkages, two terminal cyclic anhydride groups and two trivalent benzene radicals, the carbonyl groups of a cyclic anhydride and a nitrogen of an imide linkage attached to each of said radicals, the former attached to 1,2-positions of the radical, the latter attached to the 4-position of the radical and (b) 3,4:3' ,4'-benzophenonetetracarboxylic dianhydride, with 
     
     
       13. A polymer containing imide linkages as claimed in claim 12 wherein said aromatic dianhydride monomer is derived by reacting 4-aminophthalic acid 
     
     
       14. A polymer containing imide linkages as claimed in claim 13 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 2,3:6,7-napthalene tetracarboxylic dianhydride, 1,8:4,5-naphthalene tetracarboxylic dianhydride, 1,2:5,6-naphthalene tetracarboxylic dianhydride, 3,4:3', 4'-diphenyl tetracarboxylic dianhydride, 2,3:2',3'-diphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl propane dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, and 
     
     
       15. A polymer containing imide linkages as claimed in claim 13 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 1,2:4,5-benzenetetracarboxylic dianhydride and 
     
     
       16. A polymer containing imide linkages as claimed in claim 13 wherein the mole ratio of said 4-aminophthalic acid to said dianhydride containing two 
     
     
       17. A soluble amide acid-imide polymer comprising the reaction product of an aromatic dianhydride containing two imide linkages, two cyclic anhydride groups and two trivalent benzene radicals, the carbonyl groups of a cyclic anhydride and a nitrogen of an imide linkage attached to each of said radicals, the former attached to 1,2-positions of the radical, the latter attached to the 4-position of the radical, and an aromatic diamine. 
     
     
       18. A polymer as claimed in claim 17 wherein said aromatic dianhydride is derived by reacting 4-aminophthalic acid and a dianhydride having two 
     
     
       19. A polymer as claimed in claim 18 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 2,3:6,7-naphthalene tetracarboxylic dianhydride, 1,2:5,6-naphthalene tetracarboxylic dianhydride, 1,8:4,5-naphthalene tetracarboxylic dianhydride, 3,4:3',4'-diphenyltetracarboxylic dianhydride, 2,3:2',3'-diphenyl tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, and bis(3,4-dicarboxyphenyl) 
     
     
       20. A polymer as claimed in claim 18 wherein said dianhydride containing two cyclic anhydride groups is selected from the group consisting of: 1,2:4,5 benzenetetracarboxylic dianhydride and 
     
     
       21. A polymer as claimed in claim 18 wherein the mole ratio of 4-aminophthalic acid to said dianhydride containing two cyclic anhydride 
     
     
       22. A polymer as claimed in claim 17 wherein said diamine is 
     
     
       23. The polymer of claim 17 further characterized in that the amide acid 
     
     
       24. The polymer of claim 21 further characterized in that the amide acid 
     
     
       25. A polymer containing amide acid and imide linkages prepared by reacting essentially stochiometric amounts of (1) a dianhydride component comprising a mixture of dianhydrides a portion thereof comprising an aromatic dianhydride monomer containing two imide linkages, two cyclic anhydride groups and two trivalent benzene radicals, the carbonyl groups of a cyclic anhydride and a nitrogen of an imide linkage attached to each of said radicals, the former attached to 1,2-positions of the radical, the latter attached to the 4-position of the radical, and (2) at least one 
     
     
       26. A polymer in accordance with claim 22 wherein said aromatic dianhydride containing imide linkages is prepared by reacting 4-aminophthalic acid and a dianhydride containing two cyclic anhydride groups in a molar ratio of 
     
     
       27. A polymer in accordance with claim 26 wherein said dianhydride reacted with 4-aminophthalic acid is selected from the group consisting of 1, 2:4,5-benzenetetracarboxylic anhydride and 
     
     
       28. A polymer in accordance with claim 27 wherein said dianhydride component contains a dianhydride selected from the group consisting of 1,2:4,5-benzenetetracarboxylic anhydride and 
     
     
       29. A polymer in accordance with claim 28 wherein said dianhydride reacted with 4-aminophthalic acid is 1,2:4,5-benzenetetracarboxylic anhydride and wherein said dianhydride component contains 
     
     
       30. A polymer in accordance with claim 29 wherein said dianhydride 
     
     
       31. A polymer in accordance with claim 29 wherein said dianhydride component is reacted with a mixture of 4,4'-diaminophenyl ether and 
     
     
       32. The polymer of claim 25 further characterized in that said amide acid 
     
     
       33. The polymer of claim 28 further characterized in that said amide acid 
     
     
       34. The polymer of claim 31 further characterized in that said amide acid 
     
     
       35. A polymer containing imide linkages corresponding to that derived from (A) an aromatic dianhydride monomer containing imide linkages derived by reacting 4-aminophthalic acid and 3,4:3',4'-benzophenonetetracarboxylic dianhydride; and (B) 4,4'-diaminodiphenyl ether.